Derivatives of 1, 4-diamino-2-nitro-benzenes



United States Patent 3,274,249 DERIVATIVES OF 1,4-DlAMINO-2-NITRO- BENZENES Walter H. Brunner, Easton, Pa, and Alexander Halasz, N orwalk, Conn, assignors to Clairol Incorporated, New York, N.Y., a corporation of Delaware N0 Drawing. Filed Sept. 14, I964, Ser. No. 396,403

14 Claims. (Cl. 26tl573) This invention relates to novel compounds that are useful as dyes and particularly as dyes for keratinaceous materials. This application is a continuation-in-part of application Serial No. 130,213, filed July 17, 1961, and now abandoned, which in turn is a divisional application of application Serial No. 67,166, filed November 4, 1960, and now abandoned.

The novel compounds of this invention can be represented by the following generic formula:

wherein R is a hydrocarbon radical free from olefinic and acetylenic unsaturation having from 1 to about 8 carbon atoms, or a hydroxyalkyl radical having from 1 to 4 carbon atoms; and wherein R is a saturated aliphatic hydrocarbon radical, i.e., alkyl, having from 1 to 4 carbon atoms, a hydroxyalkyl radical having from 1 to 4 carbon atoms, and R" is hydrogen or hydroxyalkyl having from 1 to 4 carbon atoms, provided that R is hydroxyalkyl only when R is also hydroxyalkyl and further provided that at least one of R and R is a hydrocarbon radical. The preferred compounds of this invention are those wherein R is a hydrocarbon radical.

Illustrative of the hydrocarbon radicals represented by R in the above generic formula there can be mentioned: alkyl radicals containing from 1 to about 8 carbon atoms and preferably 1 to 4 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, n-hexyl and the like; cycloalkyl radicals such as those having from 4 to 6 carbon atoms, e.g., cyclobutyl, cyclopentyl, and cyclohexyl; the phenyl, alkylphenyl or phenalkyl radicals, e.g., benzyl, 4-methylphenyl, 4-ethylphenyl and the like; and lower alkyl substituted cycloalkyl radicals, such as 4-methylcyclohexyl, 4-ethylcyclohexyl and the like. When R is a hydroxyalkyl radical, the alkyl can be methyl, ethyl, propyl, isopropyl, butyl, etc.

The various radicals as represented by R of the generic formula can be alkyl having up to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and the like; hydroxyalkyl radicals having from 1 to 4 carbon atoms, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxy-propyl and 4-hydroxybutyl. The term hydroxyalkyl is intended to embrace both monohydroxy or polyhydroxy substituents, e.g., dihydroxy, although it is preferred that when either R or R of generic Formula I is a hydroxyalkyl, it be a monohydroxyalkyl.

R" in Formula I above may be hydrogen or hydroxyalkyl and has the value hydroxyalkyl only when R is also hydroxyalkyl. Moreover, preferably, both R" and R are the same hydroxyalkyl group, e.g., hydroxyethyl.

It can be seen from generic Formula I that bot-h R and R can be hydrocarbon radicals or only one of R and R need be a hydrocarbon radical. Illustrative of some of the combinations of R and R of novel classes of compounds represented by generic Formula I there can be mentioned those wherein: R is a monohydroxyalkyl having from 1 to 4 carbon atoms and R is an alkyl having from 1 to 4 carbon atoms; R is phenyl and R is an alkyl having from 1 to 4 carbon atoms; R is a. cycloalkyl having 4 to 6 carbon atoms, and particularly 6 carbon atoms and R is an alkyl having from 1 to 4 carbon atoms; R is an alkyl having from 1 to 4 carbon atoms and R is a monohydroxyalkyl having from 1 to 4 carbon atoms; R is an alkyl having from 1 to 4 carbon atoms and R is an alkyl having from 1 to 4 carbon atoms; R is phenyl and R is a monohydroxyalkyl having from 1 to 4 carbon atoms; R is a cycloalkyl having .from 4 to 6 carbon atoms, and particularly 6 carbon atoms and R is a monohydroxyalkyl having from 1 to 4 carbon atoms.

In addition to the above illustrated compounds the following compounds can also be mentioned:

1-methylamino-2-nitro-4-propylaminobenzene;

1-methylamino-2-nitro-4-hydroxyrnethylarninobenzene 1-methylamino-2-nitro-4-( 3 -hydroXy-propyl) aminobenzene;

1-methylamino-2-nitro-4-(2,3 -dihydroxypropyl) aminobenzene;

1-methylamino-2-nitro-4- (4-hydr0xybutyl) aminobenzene;

1-phenylamino-2-nitro-4-methylaminobenzene;

1-phenylamino-2-nitro-4-ethylaminobenzene;

1 -phenylamino-2-nitrot-butyl) aminobenzene;

1-phenylamino-2-nitro-4-hydroxymethylaminobenzene 1-phenylamino-2-nitro-4- 2-hydroxyethyl) aminobenzene l-phenylamino-2-nitro-4- 3 -hydroxypropyl) aminobenzene;

1-pheny 1arnin0-2-nitr0-4- 2,3 -dihydroxypropyl) aminobenzene;

1-cycloheXylamino-2-nitr0-4-methylaminobenzene;

1-cyclohexylamino-2-nitro-4-ethylaminobenzene;

1-cyclohexylamino-Z-nitro-4-propylaminobenzene;

1-cyclohexylamino-2-nitro-4- (n-butyl) aminobenzene;

1-cyclohexylamino-2-nitro-4-hydroxymethylaminobenzene;

1-cyclohexylamino-2-nitro-4- 2-hydroxyetl1yl) aminobenzene;

1-cyclohexylamino-2-nitro-4- 3-hydroxypropyl) aminobenzene;

1-hydroxymethylamino-2-nitro-4-methylaminobenzene;

1- 3 -hydroxypropyl) amino-2-nitro-4-methylaminobenzene;

1- 2,3 -dihydroxypropyl) amino-Z-nitro-4-methylaminobenzene;

1-hydroxymethylarnino-Z-nitro-4-ethylaminobenzene;

1- (2hydroxyethyl) a-mino-Z-nitro-4-ethylaminobenzene;

and the like.

Thecompounds of this invention can be produced by reacting a 1 secondaryamino 2 nitro-4-aminobenzene with a reactant or reactants so as to replace at least one of the hydrogen atoms of the 4-amino group with the desired radical. The 1-secondaryamino-2-nitro-4-aminobenzene reactant can be represented by the following generic formula:

H-I I-H Formula II wherein R represents the same radicals as in generic Formula I, namely a hydrocarbon radical free from olefinic and acetylenic unsaturation having from 1 to about 8 carbon atoms, or a hydroxyalkyl radical having from 1 to 4 carbon atoms. Illustrative of compounds represented by generic Formula II there can be mentioned: l-methylamino 2 nitro-4-aminobenmne; 1-(2'-hydroxyethyl) amino-Z-nitro 4 aminobenzene; l-phenylamino-Z- nitro 4 aminobenzene; '1 cyclohexylamino 2 nitro-4- aminobenzene; and the like.

The 1 se-condaryamino 2 nitro-4-alkylaminobenzene compounds of this invention can be produced by reacting a l-secondaryamino-2-nitro-4-aminobenzene with an alkylating agent. Illustratively, a 1-secondaryamino-2- nitro-4 aminobenzene, e.g., l-methylamino-2nitro-4-aminobenzene (about 60 parts by Weight) is dissolved, preferably with heating to about 65 C., in a lower alkyl monohydric alcohol (about 1,000 parts), such as methanol. An aqueous solution of a base, such as sodium carbonate (about 30 parts of sodium carbonate in 180 parts of water), is then added to the alcoholic solution and the mixture is then permitted to cool to about C., after which time a dialkyl sulfate, e.g., dimethyl sulfate (about 25 parts) is slowly added to the reaction mixture. The reaction mixture is then boiled for about two hours, with the optional addition of more of the dialkyl sulfate (e.g., about 17 parts). Generally, from about 1.5 moles to about 2 moles of the dialkyl sulfate per mole of the nitro compound is employed, and preferably 2 moles of the dialkyl sulfate. The l-secondaryamino-2-nitro-4-alkylaminobenzene which is thus produced is recovered from the reaction mixture by conventional techniques, such as fractional distillation, extraction, extractive distillation, precipitation or combinations of two or more of these techniques.

In order to prepare the novel compounds of this invention wherein the 4-amino group is substituted with at least one hydroxyalkyl group, a l-secondaryamino-Z- nitro-4-aminobenzene can be reacted with a halogen substitution product of a monohydric or polyhydric aliphatic alcohol by refluxing or simply heating above room temperature and in the presence of an aqueous solution of an acid-binding agent, such as an alkali metal hydroxide or calcium oxide. The reaction time can vary from about 4 to 6 hours, and preferably about 4 hours. Generally, molecular proportions of the nitro compound and the alcohol reactant are employed. The quantity of the acid binding agent employed is in excess of the theoretical quantity required to neutralize the acid formed, and this excess can vary from about 10% to 100% more than theory. Illustrative of the halogen substituted alcohol reactant there can be mentioned: 1-hydroxy-2-chlorethane and 1,2-dihydroxy-3-chlorpropane. The hydroxyalkyl derivative of the nitro compound can be recovered by conventional means, such as by boiling to concentrate the reaction mixture and then salting out by addition of sodium chloride.

When the l-secondaryamino radical of the compounds of generic Formula II is an alkylamino radical and it is desired to substitute the 4-amino group with a hydroxyalkyl radical to produce one of the compounds of generic Formula I, it is preferable first to react the 4-amin-o group of a Formula II compound with p-toluenesulfonyl chloride and form the tosyl derivative. In conducting this reaction a l-alkylamino compound of Formula II is first dissolved in an organic base, such as pyridine or a homologue thereof. The p-toluenesulfonyl chloride, about 1.2 to about 1.4 moles for each mole of the l-alkylamino compound of Formula II, is then added slowly at about room temperature to the organic base solution of the l-alkylamino compound of Formula II. The reaction mixture is then refluxed for about 0.5 to 1.5 hours and preferably about 1 hour to effect reaction. The reaction mixture is then poured in Water and cooled to about 20 C. to about C. in order to precipitate the tosyl derivative of the l-alkylamino compound. The precipitate is then filtered. The 1 alkylamino-2-nitro-4-tosyl aminobenzene is then dissolved in water and sodium hydroxide. The solution is cooled to about 10 C. and ethylene chlorohydrin, about 1.25 to about 2.5 moles per mole of the tosyl derivative, is then added slowly to the solution. The reaction mixture is then heated from about 50 C. to about 70 C. and preferably about 60 C. for about 3 hours to about 4 hours, and preferably 3 hours. The above mixture is then permitted to cool and the l-alkylamino-2-nitro-4-hydroxyalkylamino-tosyl compound is recovered. This tosyl product is subsequently hydrolyzed by acidification with a molar excess of sulfuric acid and permitted to remain at a temperature of about 3 C. to about 4 C. until the tosyl product is completely dissolved. The sulfate salt is then neutralized with ammonia to obtain the base form of the l-alkylamino-2- nitro-4-hydroxyalkylaminobenzene which can be recovered from the reaction mixture by conventional techniques, such as first cooling the mixture and then salting out by the addition of sodium chloride.

In order to prepare the novel compounds of this invention, wherein the 4-amino group is substituted with two hydroxyalkyl radicals, e.g., two hydroxyethyl radicals, the following process can be employed. The appropriate l-secondary-amino-2-nitr-o-4-aminobenzene is dissolved in a lower alkyl monohydric alcohol, such as ethanol, and a small quantity of water is added to the solution, e.g., from about 1 to about 12% by weight of the quantity of alcohol employed. The solution is refluxed and an alkylene oxide, e.g., ethylene oxide is bubbled into the refluxing mixture until the mixture has absorbed the desired molar quantity of the alkylene oxide, e.g., 2 moles of ethylene oxide per mole of the nitro compound when it is desired to produce the bis-hydroxyalkyl derivative. The 1 secondaryamino 2 nitro 4 [bis(hydroxyalkyl)amino]benzene is then recovered by conventional techniques, such as fractional distillation, extraction, extractive distillation, precipitation or combinations of two or more of these methods. By still another method the 1 secondary-amino 2 nitro 4 [bis(hydroxyalkyl)- amino]benzene compounds can be prepared by hydroxyalkylating an appropriate 1-secondaryamino-2-nitro-4- amino benzene in the presence of an aqueous sodium hydroxide solution.

The 1-secondaryamino-2-nitro-4-aminobenzene reactants can be produced by a number of methods including the reduction of a 1-secondaryamino-2,4-dinitrobenzene to the corresponding 1-secondaryamino-2-nitro-4-aminobenzene. The 1 second-aryamino-2,4-dinitrobenzene react-ant can be represented by the following generic formula:

H-ITI- R I TOZ Formula III wherein R represents the same radicals as in generic Formula I, namely, a hydrocarbon radical free from olefinic and acety-lenic unsaturation having from 1 to about 8 carbon atoms, or a hydroxyalkyl radical having from 1 to 4 carbon atoms. One process for the reduction of the 1-secondarya.min'o-2,4-dinitrobenzene to the corresponding l-secondaryamino-2-nitro-4-am inobenzene is by introducing about 3 moles of hydrogen into a hydrogenation apparatus maintained at about 25 to 70 C. and 2 to 3 atmospheres of pressure and containing a mixture of (a) an isopropanolic or ethanolic solution of about 1 mole of a 1-second-aryamino-2,4-dinitrobenzene; (b) a catalytically effective quantity of platinum or palladium; and (0) about 2 moles of an aqueous solution of a strong inorganic acid, such as hydrochloric or sulfuric acid, e.g., a 50% solution of H in water, to give a strongly acid reaction mixture. This hydrogenation can be carried out in less than one hour to produce the acid addition salt of the l-secondaryamino-2-nitro-4-aminobenzene. The acid addition salt is then reacted with an alkaline material to produce the free base form of the amino compound by the conventional methods well known in the art. This reduction process is illustrated in Examples 7 to 9 of this specification.

The novel compounds of this invention have utility for dyeing keratinaceous materials and particularly living human hair. When used as dyes, they possess many advantageous properties. Illustratively, they have a pronounced afiinity for the hair; they exhibit a good dyeing union with both normal and permanently waved hair, particularly gray hair; they give a wide spectrum of colors, such as that of bluish-red over a violet to a blue and when used in combination with known dyes, they can easily produce various blonde to brown shades; they lose little color upon shampooing; have good lightfastness and rubfastness; they produce bright and lustrous shades; they have good storage stability; and do not stain the scalp. A further advantage is that they do not require the use of the conventional peroxide additives, e.g., hydrogen peroxide, for color formation or fixation to the hair. Although the prior art describes certain nitro derivatives of p-phenylene diamines as hair dyes, the prior art p phenylene diamines do not have two secondary amino groups wherein at least one of the secondary amino groups carries a hydrocarbon radical. The compounds of the instant invention have many advantageous properties over the prior art compounds, and particularly in the range of colors produced; good dyetake at pH values of 7 to about 9; uniformity of dyetake between permanent waved parts of the hair and non-permanent waved parts of the hair; the ability to be removed more easily from the .hair by special treatments; and improved lightfastness, rubfastness and washfastness.

The dyeing compositions of this invention comprise neutral or alkaline aqueous solutions of the novel compounds. In addition to the water, alkalizing agent and dye, the compositions can also contain the conventional ingredients found in dyeing compositions, such as organic solvents for the dye, thickeners, detergents, gums and the like. Alkalizing agents are ordinarily added to the compositions, since the pH of the dyes varies from that of weakly acidic to about neutral.

The dyeing compositions of this invention can be applied to keratinaceous materials by the conventional techniques used in the art. Illustratively, when applied to living hair on the human head, the compositions can be applied to the hair with a brush, sponge, or other means of contact, such as dipping until the hair is properly saturated with the composition. The reaction time or time of contact of the dyeing composition with the hair is not critical and can vary over the wide range used in the hair dyeing art such as periods of about 5 minutes to about 2 hours, and preferably from about minutes to about 60 minutes. The dyeing temperature can vary over Wide limits as is conventional in the art. Thus, the dyeing temperature can vary from about room temperature, e.g., about C. to above about 60 C. and preferably from about 20 C. to about 45 C.

The dyeing compositions of this invention can be prepared by the conventional methods used in the hair dyeing art. Thus, they can be prepared by dissolving or dispersing the dye in Water of the desired concentration. Water miscible organic solvents can he employed to facilitate solution of the dye; in this event, the dye can be dissolved first in the solvent and then diluted with Water. Illustrative of the organic solvents which can be used, there can be mentioned: the lower alkyl monohydric alcohols, such as ethanol or isopropanol; lower aliphatic dihydric alcohols, e.g., propylene glycol; various polyhydric alcohols; ketones; and esters. The dispersion of the various ingredients can also be facilitated by addition of a detergent or dispersing agent, such as lauryl or myristyl sulfate or sulfonate. The water miscible organic solvents employed to facilitate solution of the dye can vary from about 1% to about 30% by weight of the composition, and preferably from about 2% to about 10%. The detergent or dispersing agent can vary from about 1% to about 30% by weight of the composition.

Any water-soluble alkalizing agent that will not interfere (i.e., is compatible) with the dye employed, and will not precipitate the dye or introduce any possibility of toxicity under the conditions of use, or injure the scalp or hide of the pelt, at its ultimate concentration in the composition to be applied to the keratinaceous material, can be used. A preliminary test of some selected alkalizing agent can be made to notes its compatibility with the dye or to introduce possibility of toxicity or injury.

Ammonium hydroxide, because of its freedom from toxicity over a wide concentration range and its economy is an acceptable alkalizing agent. However, there can be used in place of, or together with the ammonia, any other compatible ammonia derivative alkalizing agent, such as a lower alkanol-amine, such as mono-, dior triethanolam-ine, or alkyl amines or alkylenediamines, such as monoethylamine, diethylamine, propylamine, dipropylamine or propylene diarnine or a heterocyclic amine, such as morpholine. Any of these ammonia derivative alkalizing agents as well as ammonium hydroxide may be broadly referred to as an ammonium alkalizant.

Also, as alkalizing agent, any alkaline earth hydroxide, for example, calcium hydroxide or magnesium hydroxide, can be used up to the limit of its water stability and at any concentration that fails to produce a precipitate with any of the components of the composition. The dissolved alkaline earth hydroxides are preferred over the alkali metal hydroxides, such as sodium hydroxide, or potassium hydroxide, or carbonates, such as sodium carbonate and bicarbonate, any of which can also be used so long as their ultimate concentration in the final dyeing solution is below that which might possibly irritate the scalp, or injure the hide of the fur pelt.

The quantity of the various ingredients in the dyeing compositions of this invention can vary over a wide range. The novel dyes of this invention can be employed in the conventional concentrations used in the dyeing of the various keratinaceous materials. Illustratively, tinctorially effective quantities can vary from less than about 0.01% to greater than about 10% by Weight of the aqueous solution. In the dyeing of living human hair the concentration of the dye will preferably vary from about 0.05% to about 5% by weight of the aqueous solution, and particularly from about 0.1% to about 3%. Any selected compatible alkalizing agent should be used to give a pH of about 7 or 7.5 to about 12, and preferably a pH of about 7.5 or 8 to about 11. The quantity of the alkalizing agent employed can vary over a wide range depending on the dye and particular alkalizing agent employed. Thus the alkalizing agent can vary from less than about 0.1% to about 5% and preferably from about 0.5% to about 2% by weight of the aqueous solution. The water content of the composition is ordinarily the major constituent and can vary over a wide range dependent in large measure on the quantity of other additives, such as solvents.

The dyes of this invention are water dispersible in the usual generic sense as embracing true solutions of the dyes in water or any aqueous medium within the bounds of the invention, as Well as stable homogeneous colloidal solutions of them in such aqueous medium. Thus, the aqueous medium includes the aqueous alkaline medium. It includes also any aqueous medium containing, for example, a suflicient amount of a compound, e.g., ethanol employed as a common solvent to enhance the solution of the dye or some other organic material. The compositions can be formulated as solutions, gels, emulsions, dispersions, and the like.

. dropwise to the mixture.

The following examples are illustrative of the invention. The term parts as used in the examples and specification refers to parts by weight, unless otherwise specified.

EXAMPLE 1 Preparation of l-(2'-hydr0xyethyl)amino- 2-nitro-4-methylaminobenzene Sixty parts of '1-(2-hydroxyethyl)amino-2-nitro-4- aminobenzene were dissolved at 60 C. to 70 C. in 1,000 parts of methanol. An aqueous solution of 30 parts of sodium carbonate in 180 parts of water was then added to the methanolic solution. After cooling the mixture to 10 C., 25 parts of dimethyl sulfate was added dropwise. The mixture was then boiled. After boiling for 1 hour, 17 parts of dimethyl sulfate was added dropwise and boiling was continued for another hour to produce the 1 (2- hydnoxyethyl amino-2-nitro-4-methylaminobenzene. This product was recovered from the reaction mixture by distilling off the methanol, digesting the residue with 100 parts of water, and finally filtering the reaction mixture to recover the product as a precipitate. The product, l-(2-hydroxyethyl) amino-2-nitro-4 methylaminobenzene was recrystallized in ethyl acetate and found to have a purple color and a melting point of 96.5 C.

EXAMPLE 2 Preparation 09 I-methylamino-Z-nitro- 4-methylaminobenzene l-methylarnino-Z-nitro 4 aminobenzene (33.4 parts) were dissolved at 60 C. to 70 C. in 660 parts of methanol. An aqueous solution of 20 parts of sodium carbonate in 120 parts of water was added to the methanolic solution and the mixture was permitted .to cool to 20 C. and 26.5 parts of dimethyl sulfate was then added The mixture was then boiled for 5 hours. The methanol was distilled off and the concentrated solution of the 1-methylamino-2-nitro-4-methylaminobenzene product was digested with 100 parts of water. After the mixture was cooled, it was filtered and the product was recovered from the reaction mixture as the precipitate. The l-methylamino-Z nitrto 4 methylaminobenzene crystals had a violet color and a melting point of 8182 C.

EXAMPLE 3 Production of l-methylamino-Z-nz'tro- 4-(2'-hydr0xyethyl)-aminobenzene l-methylamino-Z-nitro 4 aminobenzene (66.8 parts) was dissolved in 450 parts of pyridine. At approximately 20 C., 100 parts of p-toluene sulfonyl chloride was added slowly. The bath was then boiled for one hour. The red color of the solution at the beginning was changed to yellow. The solution was poured into 2,000 parts of water and ice was added for cooling. The tosyl derivative which was thus produced was in the form of red crystals which were filtered and dissolved in 1,500 parts of water and 25 parts sodium hydroxide. This gave a purple solution. The solution after filtration was acidified with 65 parts of concentrated hydrochloric acid (38% by weight HCl content) to a clear blue congo paper reaction. It was then filtered, washed acid free, and dried in vacuo. This tosyl derivative, 1-methylamino-2-nitro-4-tosylaminobenzene had a melting point of 160 C. The l-methylamino-2-nitro-4-tosylarninobenzene (125.4 parts) was dissolved in 1,500 parts of water and 15.6 parts of sodium hydroxide. The solution was cooled to C. and 37.5 parts ethylene chlorohydrin were added dropwise over a period of about 1.5 hours. After an additional half hour stirring at 10 C., the batch was heated at 95 C. to 98 C. for 2 hours. The pH was 6.8. After cooling the orange crystals of the 1-methylamino-2-nitro-4-hydroxyethylaminotosyl compound was filtered. The l-methylamino- 2-nitro-4-hydroxyethylaminotosyl compound was dried and pulverized, and 81.1 parts of this tosyl product was dissolved in 370 parts of sulfuric acid (50% by weight) at a temperature of about 2 C. This mixture was poured in 300 parts of ice, giving a yellow solution of the dye sulfate; and by neutralizing with ammonia, a bluish violet dye, l-methylamino-Z nitro 4 (2-hydroxyethyl)aminobenzene, was obtained which had a melting point of to 101 C.

EXAMPLE 4 Preparation of J-methylamino-Z-nitro- 4-[bis(2'-hydroxyethyl)amino]benzene l-methylamino-2-nitro-4-aminobenzene, 33.4 parts (0.2 mole) were dissolved in a mixture of 350 parts ethanol and 50 parts of water This solution was refluxed and a current of ethylene oxide, 17.8 parts (0.4 mole) Was bubbled in the reaction mixture. The reaction mixture was then steam distilled to eliminate the ethanol. Upon permitting the reaction mixture to cool the l'methylamino-2 nitro-4- [bis 2-hydroxyethyl) amino] benzene crystallized out as blue crystals which were recovered by filtration. The melting point of this material was 101 to 102 C.

EXAMPLE 5 Preparation of J -phenylamin0-2-nitr0-4- 2'-hydroxyethyl -aln inobenzene To 1 gram of l-phenylamino-2-nitro-4-aminobenzene there were added 100 ml. of l-hydroxy-Z-chlorethane. This mixture was then refluxed and 1100 grams of 25% by weight sodium hydroxide solution was added slowly over a period of about one hour. The mixture was steam distilled and then cooled and the 1-phenylamino-2-nitro- 4-(2-hydroxyethyl)aminobenzene was extracted from the reaction mixture with ethyl acetate. The ethyl acetate was evaporated to leave the 1-phenylamino-2-nitro-4-(2- hydroxyethyl)aminobenzene as purple-violet crystals.

EXAMPLE 6 Preparation of 1-cyclohexylamino-2-nitro-4- (2'-hydroxyethyl)aminobenzene To 1 gram of 1-cyclohexylamino-2-nitro-4-aminobenzene, (2-nitro-4-arnino-N-cyclohexyl aniline), there was added 100 ml. of l-hydroxy-Z-chlorethane. The mixture was refluxed and there was added 100 grams of an aqueous solution of sodium hydroxide (25% by weight NaOH content) over a period of 1 hour during refluxing. The mixture was permitted to reflux for an additional 0.5 hour and then steam distilled, cooled, and the l-cyclohexyla-mino-2-nitro-4-(2'-hydroxyethyl) aminobenzene was extracted from the reaction mixture with ethyl acetate. The ethyl acetate extract was heated to evaporate the ethyl acetate to leave the product as bluish-purple crystals.

EXAMPLE 7 Reduction of 1-methylamino-2,4-dinitrobenzene to 1-metlzylamino-2-nitr0-4-amin0benzene In a hydrogenation apparatus there were charged 0.5 gram of 5% platinum on charcoal, a mixture of 9.85 grams (0.05 mole) of pulverized N-methyl-2,4-dinitroaniline, also referred to in this specification as l-methylamino-2,4-dinitrobenzene, in 200 ml. of ethanol (96% ethanol content) and 20 ml. of concentrated (38%) hydrochloric acid. The reaction mixture was heated to 60 C. and held at this temperature while there was introduced into the reaction chamber, with constant shaking 0.303 gram (0.15 mole) of hydrogen at a pressure of 50 to 40 p.s.i. (over a period of about 30 minutes). After cooling the reaction mixture to room temperature, a mixture of the catalyst and the hydrochloride of the nitroaniline separated as yellow crystals. These crystals were filtered off, dissolved in 50 ml. of 'hot water and the undissolved catalyst filtered off. The filtrate was cooled and the resulting acid addition salt of l-methylamino-2-nitro-4-aminobenzene which precipitated out of solution was recovered by filtration. The salt was alkalized with aqueous ammonia to obtain the free base form of the aminoaniline product, i.e., l-methylamino-Z-nitro- 4-aminobenzene as dark red crystals.

EXAMPLE 8 Reduction of 1-phenylamin0-2,4-dinizrobenzene to I-phenylamin-2-nitr0-4-aminobenzene Into a hydrogenation apparatus there were charged 0.2 gram of platinum on charcoal 2 ml. of water, 20 ml. of isopropanol, 13.2 grams mole) N-phenyl 2,4- dinitroaniline, also referred to in this specification as 1- phenylamino-2,4-dinitrobenzene, and an additional 80 ml. of isopropanol and 20 grams of a 50% aqueous solution of H 80 The temperature of the reaction mixture was brought up to about 65 C. and then there was introduced into the reactor at a pressure of 50 to 40 p.s.i. about .303 gram (0.15 mole) of hydrogen over a period of 17 minutes. The temperature of the reaction mixture at the end of the 17 minute period was 52 C. The reaction mixture was permitted to cool, the autoclave was opened and the sulfate salt of 1-phenyla mino-2-nitro-4-aminobenzene which was produced by the hydrogenation was filtered off as a precipitate. The sulfate salt was subsequently alkalized and separated to obtain the l-phenylamino-Z- nitro-4-aminobenzene as red crystals.

EXAMPLE 9 Reduction of 1-(2'-hya'r0xyethyl)amino-2,4-a'initr0benlane to 1-(2'-hydr0xyethyl)amin0-2-nitr0-4-aminobenzene In a hydrogenation apparatus there were placed: 0.5 gram of 10% palladium on charcoal, 20 ml. of concentration hydrochloric acid (38%) and a solution of 22.7 grams (0.10 mole) of N-(2-hydroxyethyl)2,4-dinitroan-iline, also referred to in this specification as 1-(2'-hydroxyethyl)amino-2,4-dinitrobenzene, in 150 ml, of ethanol. This reaction mixture was hydrogenated at a pressure of 50 to 30 p.s.i. and a temperature of 60 C. After adsorption by the reaction mixture of 0.3 mole of hydrogen, the apparatus was permitted to cool. The yellow hydrochloric acid salt of 1-(2'-hydr0xyethyl)amino-2-nitro-4- aminobenzene was separated from the catalyst by dissolving in hot water. The free base l-(2'-hydroxyethyl)ami no-2-nitro-4-aminobenzene was obtained by neutralizing the salt with ammonia.

EXAMPLE l0 Dyeing of hair with 1-methylamin0-2-nitr0-4-[bis(2'-hydr0xyethyl)amin0]benzene (product of Example 4) l methylamino 2 nitro 4 [bis(2' hydroxyethyl)amino]benzene of Example 4, 1 gram, was dissolved in a mixture of 20 ml. of isopropanol, about 2 00 ml. of water, 2 grams of monoethanolamine, 1 gram of triethanolamine, 1 gram of polyacrylic acid and 1 gram of glycerol at 50 C. This composition was heated to about 35 C. to 37 C. and then applied to gray hair. After about 20 minutes, the hair was thoroughly rinsed and washed with soap and water. The hair was colored blue by the composition and the resulting shade was rubfast and not removable by washing with soap and water.

EXAMPLE 1 l Dyeing of hair with 1-methylamin0-2-nitr0-4- (2-hydr0xyethyl)aminobenzene The hair was dyed to a EXAMPLE 12 By employing the procedure and composition, including the various quantities of ingredients except for the substitution of the following dyes in place of the l-methylamino- 2-nitro-4-(2'-hydroxyethyl)aminobenzene of Example 11 there are produced the following colors on gray hair: 1 (2-hydroxyethyl) amino-Z-nitro-4-methylaminobenzene produces a blue color; 1-methylamino-2-nitro-4methylaminobenzene produces a reddish purple color; l-methylamino 2 nitro-4-[b-is(2'-hydroxyethyl)amino1benzene produces a blue color; l-phenylamino-Z-nitro-4-(2-ihydroxyethyl) aminobenzene produces a violet color; and l-cyclohexylamino 2 nitro-4-(2'-hydroxyethyl)aminobenzene produces a violet color.

EXAMPLE 13 Preparation of 1-methylamino-2-nitr0-4-[bis (2-hydr0xyethyl) amino] benzene One mole of 1-methylamino-2-nitro-4-aminobenzene was admixed with 10 moles of 1-1hydroxy-2-chlorethane in 200 grams of water. This mixture was then heated to about to 98 C. and maintained at that temperature while 4 moles of a 25% aqueous solution of sodium hydroxide was added dropwise to the mixture. The mixture was then cooled and 100 grams of sodium chloride was added to the mixture to salt out the l-methylamino- 2-nitro-4-[bis(2' hydroxyethyl)amino]benzene as blue crystals. The mixture was then filtered to recover this glycol derivative.

Illustrative of'speciaic novel compounds of this invention there can be mentioned:

1 H-N-orr.

I ONO:

HNC H2C H2 OH 1-methy1amin0-2-nitr0-4- (2-hydroxyethyl) aminobenzene HNC H C H: C Hz 0 H 1-methy1amin0-2-nitro-4- [bis (2-hydroxyethy1) amino] benzene (4) H-N'CH2OH3 I @NO:

HNCH

1- 2 -hydroxyethy1)amin0-2-nitro-4-methylaminobenzene Although the invention has been described with reference to specific forms thereof, it will be understood that many changes and modifications may be made without departing from the spirit of this invention.

What is claimed is:

1. Compounds of the formula:

wherein R is a member selected from the group consisting of alkyl of 1 to 8 carbon atoms, cycloalkyl of 4 to 6 carbon atoms, aryl, alkaryl and aralkyl of 6 to 8 carbon atoms and mono'hydroxy alkyl having from 1 to 4 carbon atoms; and R is member selected from the group consisting of a saturated aliphatic hydrocarbon radical having from 1 to 4 carbon atoms and a hydroxyalkyl radical having from 1 to 4 carbon atoms and R is selected from the group consisting of hydrogen and hydroxyalkyl having from 1 to 4 carbon atoms, provided that R is hydroxyalkyl only when R is also hydroxyalkyl and further provided that at least one of R and R is a hydrocarbon radical.

2. Compounds according to claim 1 wherein both R and R of the formula are alkyl radicals having form 1 to 4 carbon atoms and R is hydrogen.

3. Compounds according to claim 1 wherein R of the formula represents an alkyl radical having from '1 to 4 carbon atoms, R represents a monohydroxyalkyl radical having from 1 to 4 carbon atoms and R is hydrogen.

4. Compounds according to claim 1 'wherein R of the formula represents an alkyl radical having from 1 to 4 carbon atoms and R and R are the same hydroxyalkyl radical.

5. Compounds according to claim 1 wherein R of the formula represents an alkyl radical having from 1 to 4 carbon atoms and R and R each represent the hydroxyethyl radical.

6. Compounds according to claim 1 wherein R is a monohydroxyalkyl radical having from 1 to 4 carbon atoms, R is an alkyl radical having from 1 to 4 carbon atoms and R .is hydrogen.

7. Compounds according to claim 1 wherein -R is the phenyl radical and R is a monohydroxyalkyl radical having from 1 to 4 carbon atoms and R is hydrogen.

8. Compounds according to claim 1 wherein R is the cyclo heXyl radical and R is a monoihydroxya'l-kyl radical having from 1 to 4 carbon atoms and R is hydrogen.

9. 1 methylamino-2-nitro-4-(2-l1ydroxyethyl)aminobenzene.

10. 1 (2-hydroXyethyl) amino-2-nitrio-4-methylaminobenzene.

11. 1-methylamino-2-nitro-4anethylaminobenzene.

12. 1-phenylamino-2-nitro-4-(2' hydroxyet-hyD-a-mino- 0 benzene.

References Cited by the Examiner UNITED STATES PATENTS 8/ 1954 Marschall 26057 3 XR *6/1 6 Eckardt 2605'73 XR 4/1963 Brunner et a1. 2'60580 OTHER REFERENCES Ram-age et val.: Journal Chemical Society London, 1952, pages 4407 and 4409.

Ridd et -al.: Journal Chem. Soc. London, 1960, pages 1 363-9.

CHARLES B. PARKER, Primary Examiner.

ROBERT V. HINES, Examiner. 

1. COMPOUNDS OF THE FORMULA: 